Preparation method of polymer

ABSTRACT

The present application can provide a preparation method that can effectively produce a polymer having desired molecular weight characteristics and solubility in a solvent, and having a monomer composition, which is designed freely and variously according to the purpose, without unnecessary components with excellent polymerization efficiency and conversion rates, and a dispersion comprising the polymer formed by the preparation method.

FIELD

The present application relates to a method for preparing a polymer anda polymer prepared by the preparation method.

BACKGROUND

Various methods of synthesizing polythiophene which is a conductivepolymer are known, and representative methods are a method of using anoxidation reaction and a method of using a radical reaction.

In the method of using an oxidation reaction, thiophene monomersdissolved or dispersed in a solvent are oxidized, and then polythiopheneis produced through a coupling reaction between the oxidized monomers.In this method, the polymerization is performed by adding an oxidant toa solvent and applying an external magnetic field thereto, but thepolymer produced by the polymerization is in a doping state, and thus aphenomenon that polymerized chains tend to bind easily to each otheroccurs, whereby there is a problem that the solubility in the solvent islowered as the polymerization proceeds. Accordingly, it is difficult toobtain a high molecular weight product because the product having amolecular weight of a certain level or more is precipitated.

A method for preparing a conductive polymer by applying a metal ligandcatalyst is also known, and in this method, oxygen and water must notonly be sufficiently removed during the polymerization process, but alsotheir inflow must be blocked during the reaction, so that the process iscomplicated and it is also not easy to completely remove the appliedcatalyst after the polymer polymerization.

A method for preparing a polymer by inducing an oxidation reactionthrough light irradiation is also known, but in this method, it is alsodifficult to obtain a high molecular weight product, where a redoxcatalyst is required for polymerization, but it is also difficult toremove the catalyst in the product.

SUMMARY

The present application relates to a method for preparing a polymer, anda polymer. It is one object of the present application to provide apreparation method capable of preparing a desired polymer with excellentpolymerization efficiency and conversion rates without consumption ormodulation in the polymerization process. It is another object of thepresent application to provide a method for preparing a polymer having alarge molecular weight of a desired level and exhibiting excellentsolubility in various solvents. It is another object of the presentapplication to provide a method for preparing a polymer, in which use ofa catalyst is unnecessary or the use thereof can be minimized so thatthe amount of the catalyst in the product can be minimized orsubstantially eliminated. It is another object of the presentapplication to provide a method for preparing a polymer that can easilyachieve copolymerization between various kinds of monomers. It isanother object of the present application to provide a polymerdispersion comprising the polymer thus prepared.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is ¹H-NMR results for Synthesis Example 1, compound 1.

FIG. 2 is ¹H-NMR results for Synthesis Example 2, compound 2.

FIG. 3 is ¹H-NMR results for Synthesis Example 3, compound 3.

FIG. 4 is ¹H-NMR results for Synthesis Example 4, compound 4.

FIG. 5 is UV-vis absorbance spectra of Example 1.

FIG. 6 is GPC analysis results of Example 1.

FIG. 7 is UV-vis spectra identified in Example 12.

FIG. 8 is GPC spectra data for Example 2.

FIG. 9 is further GPC spectra data for Example 2.

FIG. 10 is ¹H-NMR results of a polymer formed in Example 2.

FIG. 11 is UV-vis absorbance spectra of Example 3.

FIG. 12 is UV-vis absorbance spectra of Example 4.

FIG. 13 is UV-vis absorbance spectra of Example 5.

FIG. 14 is ¹H-NMR results of the polymers synthesized in Example 3.

FIG. 15 is ¹H-NMR results of the polymers synthesized in Example 4.

FIG. 16 is ¹H-NMR results of the polymers synthesized in Example 5.

FIG. 17 is GPC spectra data for Example 3.

DETAILED DESCRIPTION

Among physical properties mentioned in this specification, when themeasured temperature and/or pressure affects the physical propertyvalue, the relevant physical property means a physical property measuredat room temperature and/or normal pressure, unless otherwise specified.

In the present application, the term room temperature is a naturaltemperature without warming or cooling, which may mean, for example, anytemperature in a range of about 10° C. to about 30° C., or a temperatureof 25° C. or 23° C. or so.

In the present application, the term normal pressure is a pressure whenit is not particularly reduced or increased, which may be about oneatmosphere or so, usually, such as atmospheric pressure.

In one example, the method for preparing a polymer of the presentapplication may be, for example, a method for preparing a conductivepolymer, and may be, for example, a method for preparing polythiophene.In this specification, the term polythiophene means a polymer containingpolymerized units of thiophene series monomers in an amount of about 50mol % or more, 55 mol % or more, 60 mol % or more, 65 mol % or more, 70mol % or more, 75 mol % or more, 80 mol % or more, 85 mol % or more, or90 mol % or more, relative to the entire polymerized unit of thepolymer. The upper limit of the polymerized unit ratio of the thiopheneseries monomers in the polythiophene is not particularly limited, whichmay be, for example, 100 mol % or less, 95 mol % or less, or about 90mol % or less or so.

The thiophene series monomer may be represented by, for example, Formula1 below.

In Formula 1, R₁ and R₂ are each independently hydrogen, an alkyl group,an alkenyl group, an alkynyl group, an alkoxy group, an alkylcarbonylgroup, an arylcarbonyl group, an arylcarbonyloxy group, analkylcarbonyloxy group, a carboxyl group or an aryl group, or are linkedto each other to form a ring structure, and R₃ and R₄ are eachindependently hydrogen, a halogen atom, an alkyl group, an alkenylgroup, an alkynyl group, an alkoxy group or an aryl group, and at leastone of R₃ and R₄ is a halogen atom.

In the present application, the term alkyl group, alkylene group oralkoxy group may mean a linear or branched alkyl group, alkylene groupor alkoxy group, having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, or may meana cyclic alkyl group, alkylene group or alkoxy group, having 3 to 20carbon atoms, 3 to 16 carbon atoms, 3 to 12 carbon atoms, 3 to 8 carbonatoms or 3 to 6 carbon atoms, unless otherwise specified.

In the present application, the term alkenyl group, alkynylene group,alkynyl group or alkynylene group may mean a linear or branched alkenylgroup or alkynyl group, having 2 to 20 carbon atoms, 2 to 16 carbonatoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms or 2 to 4 carbon atoms,or may mean a cyclic alkenyl group or alkynyl group, having 3 to 20carbon atoms, 3 to 16 carbon atoms, 3 to 12 carbon atoms, 3 to 8 carbonatoms or 3 to 6 carbon atoms, unless otherwise specified.

In this specification, the term aryl group or arylene group means amonovalent or divalent substituent derived from benzene or a derivativethereof a compound in which two benzenes are bonded while sharing one ortwo carbon atoms, or a derivative thereof; a compound in which twobenzenes are bonded by an arbitrary linker, or a derivative thereof, ora compound in which three or more benzene compounds are bonded, whereinthe benzene compounds bonded to each other are bonded while sharing oneor two carbon atoms with each other, or linked by an arbitrary linker,or a derivative thereof. The aryl group may be an aryl group or arylenegroup having 6 to 30 carbon atoms, 6 to 24 carbon atoms, 6 to 18 carbonatoms or 6 to 12 carbon atoms. The aryl group or arylene group may alsobe optionally substituted by one or more substituents.

The alkyl group, alkylene group, alkoxy group, alkenyl group, alkynylenegroup, alkynyl group, alkynylene group, arylene group and/or aryl groupmay also be optionally substituted with one or more substituents, wherethe substituent can be exemplified by a glycidyl group, a glycidoxyalkylgroup, an acryloyl group, a methacryloyl group, an acryloyloxy group, amethacryloyloxy group, a hydroxy group, a carboxyl group, an epoxygroup, an alkyl group, an alkylene group, an alkoxy group, an alkenylgroup, an alkynylene group, an alkynyl group, an alkynylene group and/oran aryl group, and the like, but is not limited thereto.

At least one or two of R₃ and R₄ in Formula 1 is a halogen atom. Thehalogen atom included in Formula 1 can be exemplified by fluorine,chlorine, bromine or iodine, and the like, and it may be suitablyiodine.

In the preparation method of the present application, a radical may begenerated at R3 and/or R4 moiety which is the halogen atom, andsubsequently the polymerization reaction may proceed.

In one example, R₁ and R₂ of Formula 1 may be linked to each other toform a ring structure. In this case, the monomer of Formula 1 above maybe represented by Formula 2 below.

In Formula 2, R₃ and R₄ may be the halogen atoms, and L may be a chainforming the ring structure.

Here, the chain may have 3 to 10 chain forming atoms. Chain formingatoms are atoms forming a chain of L, and an example thereof includescarbon, oxygen, nitrogen or sulfur, where in a suitable example, it maybe carbon or oxygen. In defining the number of chain forming atoms,atoms other than the atoms present at the sites forming the chain arenot considered. For example, the chain may also be optionallysubstituted by one or more substituents, and in this case, the number ofatoms present in the substituent is not included in the number of chainforming atoms, and when the chain forming atom is carbon or nitrogen towhich hydrogen atoms are boned, the hydrogen atoms are not counted aschain forming atoms. In addition, when two or more of oxygen or sulfureach exist as the chain forming atoms, the oxygen or sulfur does notexist adjacent to each other in the chain structure.

In the compound of Formula 1 above, at least one of R₁ and R₂ may be asubstituent including an oxygen atom, or the ring structure formed bylinking R₁ and R₂ of Formula 1 may contain an oxygen atom.

That is, in Formula 1, at least one or both of R₁ and R₂ may be analkoxy group, an alkylcarbonyl group, an arylcarbonyl group, anarylcarbonyloxy group, an alkylcarbonyloxy group or a carboxyl group,which may be, suitably, an alkoxy group.

In addition, when R₁ and R₂ in Formula 1 are linked to each other toform a ring structure, the chain by R₁ and R₂ forming a ring structure(for example, L in Formula 2) may contain at least an oxygen atom. Inthis case, the number of oxygen atoms included in the chain is one, or 2or more, and the upper limit thereof is not particularly limited, butis, for example, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less,5 or less, 4 or less, 3 or less, or 2 or less. In addition, when two ormore oxygen atoms exist in the chain, the relevant oxygen and oxygen maynot be adjacent to each other. In other words, for example, a carbon ornitrogen atom may be present between the two or more oxygen atoms, andsuitably, a carbon atom may be present.

In a suitable example, the chain by R₁ and R₂ may have 3 to 10 chainforming atoms, where the chain forming atom is carbon or oxygen, but atleast one or 2 to 5, 2 to 4, 2 to 3 or 2 chain forming atoms may beoxygen atoms which are not adjacent to each other.

As the compound having such a form lowers the oxidation potential of thecompound by unshared electron pairs of the oxygen atom, thepolymerization reaction can proceed more effectively.

For example, the monomer of Formula 1 above including oxygen atoms maybe represented by any one of Formulas 3 to 5 below.

In Formula 3, R₃ and R₄ are each independently hydrogen, an alkyl group,an alkenyl group, an alkynyl group, an alkylcarbonyl group, anarylcarbonyl group or an aryl group, or are linked to each other to forma ring structure, and R₁ and R₂ are each independently hydrogen, ahalogen atom, an alkyl group, an alkenyl group, an alkynyl group, analkoxy group or an aryl group, and at least one of R₁ and R₂ is ahalogen atom.

In Formula 4 or 5, R₃ and R₄ are each independently hydrogen, an alkylgroup, an alkenyl group, an alkynyl group, an alkoxy group, analkylcarbonyl group, an arylcarbonyl group, an arylcarbonyloxy group, analkylcarbonyloxy group, a carboxyl group or an aryl group, R₁ and R₂ areeach independently hydrogen, a halogen atom, an alkyl group, an alkenylgroup, an alkynyl group, an alkoxy group or an aryl group, at least oneof R₁ and R₂ is a halogen atom, and m is a number in a range of 1 to 4.

In Formula 3, R₃ and R₄ may be, suitably, an alkyl group, an alkenylgroup, an alkynyl group or an aryl group, or an alkyl group, and inFormulas 3 to 5, suitable examples for R₁ and R₂ are the same as R₃ andR₄ in Formula 1.

As the thiophene series monomers to be applied to the polymerizationprocess in the present application, all the above-described monomers aremonomers containing a halogen atom, which may serve as an initiator or aradical generating source of the polymerization process. In one example,the thiophene series monomer applied in the polymerization process ofthe present application may be a mixture of a monomer containing ahalogen atom and a monomer containing no halogen atom. By applying sucha monomer composition, the reaction can be controlled so that aphotoarylation mechanism is superior to a photocondensation mechanism inthe polymerization mechanism, and as a result, it is possible to form ahigh molecular weight conductive polymer more effectively.

Thus, in one example, the mixture applied to the polymerization processmay comprise a non-halogenated thiophene series monomer, which may be,for example, a compound of Formula 6 below.

In Formula 6, R₁ and R₂ are each independently hydrogen, an alkyl group,an alkenyl group, an alkynyl group, an alkoxy group, an alkylcarbonylgroup, an arylcarbonyl group, an arylcarbonyloxy group, analkylcarbonyloxy group, a carboxyl group or an aryl group, or are linkedto each other to form a ring structure, and R₃ and R₄ are eachindependently hydrogen, an alkyl group, an alkenyl group, an alkynylgroup, an alkoxy group or an aryl group, and at least one of R₃ and R₄is a hydrogen atom.

The details for such non-halogenated monomers are the same as thedetails described for the halogenated monomers, except that they containno halogen.

For example, in Formula 6, at least one or two of R₃ and R₄ are hydrogenatoms other than halogen atoms.

Furthermore, in one example, when R₁ and R₂ of Formula 6 are linked toeach other to form a ring structure, the monomer of Formula 6 may berepresented by Formula 7 below.

In Formula 7, R₃ and R₄ may be the hydrogen atoms, and L may be a chainforming the ring structure, where the details for the chain are the sameas in the case of Formula 2.

In the compound of Formula 6 above, at least one of R₁ and R₂ may be asubstituent including an oxygen atom, or the ring structure formed bylinking R₁ and R₂ of Formula 1 may include an oxygen atom. That is, inFormula 6, at least one or both of R₁ and R₂ may be an alkoxy group, analkylcarbonyl group, an arylcarbonyl group, an arylcarbonyloxy group, analkylcarbonyloxy group or a carboxyl group, and may be, suitably, analkoxy group.

In addition, when R₁ and R₂ in Formula 6 are linked to each other toform a ring structure, the chain by R₁ and R₂ forming a ring structure(for example, L in Formula 2) may contain at least an oxygen atom. Inthis case, the number of oxygen atoms included in the chain is one, or 2or more, and the upper limit thereof is not particularly limited, butis, for example, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less,5 or less, 4 or less, 3 or less, or 2 or less. In addition, when two ormore oxygen atoms exist in the chain, the relevant oxygen and oxygen maynot be adjacent to each other. In other words, for example, a carbon ornitrogen atom may be present between the two or more oxygen atoms, andsuitably, a carbon atom may be present. In a suitable example, the chainby R₁ and R₂ may have 3 to 10 chain forming atoms, where the chainforming atom is carbon or oxygen, but at least one or 2 to 5, 2 to 4, 2to 3 or 2 chain forming atoms may be oxygen atoms which are not adjacentto each other. The advantages of the compound having such a form are asdescribed above.

For example, the monomer of Formula 6 including oxygen atoms may berepresented by any one of Formulas 8 to 10 below.

In Formula 8, R₃ and R₄ are each independently hydrogen, an alkyl group,an alkenyl group, an alkynyl group, an alkylcarbonyl group, anarylcarbonyl group or an aryl group, or are linked to each other to forma ring structure, and R₁ and R₂ are each independently hydrogen, analkyl group, an alkenyl group, an alkynyl group, an alkoxy group or anaryl group, and at least one of R₁ and R₂ is a hydrogen atom.

In Formula 9 or 10, R₃ and R₄ are each independently hydrogen, an alkylgroup, an alkenyl group, an alkynyl group, an alkoxy group, analkylcarbonyl group, an arylcarbonyl group, an arylcarbonyloxy group, analkylcarbonyloxy group, a carboxyl group or an aryl group, R₁ and R₂ areeach independently hydrogen, an alkyl group, an alkenyl group, analkynyl group, an alkoxy group or an aryl group, at least one of R₁ andR₂ is a hydrogen atom, and m is a number in a range of 1 to 4.

In Formula 8, R₃ and R₄ may be, suitably, an alkyl group, an alkenylgroup, an alkynyl group or an aryl group, or an alkyl group, and inFormulas 8 to 10, suitable examples for R₁ and R₂ are the same as R₃ andR₄ in Formula 1.

As above, when the mixture of the halogenated thiophene monomer and thenon-halogenated thiophene monomer is applied as the monomer, the ratiobetween them is not particularly limited. For the proper progress ofpolymerization, for example, based on the compounds of Formulas 1 and 6,the ratio (Halo/(Halo+H)) of the molar number (Halo) of halogen atomscontained in R₃ and R₄ of Formula 1 and the molar number (H) of hydrogenatoms contained in R₃ and R₄ of the compound of Formula 6 may be in arange of 0.001 to 99. In another example, the ratio (Halo/(Halo+H)) maybe about 0.01 or more, 0.05 or more, 0.1 or more, 0.15 or more, 0.2 ormore, 0.25 or more, 0.3 or more, 0.35 or more, 0.4 or more, 0.45 ormore, or 0.5 or more, or may be 95 or less, 90 or less, 85 or less, 80or less, 75 or less, 70 or less, 65 or less, 60 or less, 55 or less, 50or less, 45 or less, 40 or less, 35 or less, 30 or less, 25 or less, 20or less, 15 or less, or 10 or less. In this range, the polymerizationcan be performed effectively to obtain a high molecular weight product.

Among the matters on the molar number ratios of halogen atoms andhydrogen atoms based on the compounds of Formulas 1 and 6, the matter onthe molar number ratios of halogen atoms and hydrogen atoms based on R₃and R₄ of Formulas 1 and 6 is equally applied to halogen atoms andhydrogen atoms of R₃ and R₄ in Formulas 2 and 7, and equally applied tohalogen atoms and hydrogen atoms of R₁ and R₂ in Formulas 3 to 5 andFormulas 8 to 10.

That is, in the entire thiophene-based monomer that the polymerizationreaction proceeds, the ratio (Halo/(Halo+H)) of the molar number (Halo)of halogen atoms included in R₃ and R₄ of Formulas 1 and/or 2, and/or R₁and R₂ of Formulas 3 to 5, and the molar number (H) of hydrogen atomsincluded in R₃ and R₄ of the compound of Formulas 6 and/or 7, and/or R₁and R₂ of Formulas 8 to 10 may satisfy the above range.

The preparation method of the present application may comprise a step ofirradiating it with light in a state where such a thiophene seriesmonomer is dissolved in a solvent.

In this process, a radical is generated at the site where the halogenatom of the thiophene series monomer is present, and a chain reactionmay occur to generate a polymer. If necessary, other monomers may alsobe present in the solvent in addition to the thiophene series monomer.

Therefore, the preparation method of the present application comprises astep of irradiating a mixture containing a monomer of Formula 1 above asthe thiophene series monomer and a solvent with light.

In a first aspect of the present application, as the solvent applied inthe preparation method, a solvent containing no hydrogen atom may beapplied.

The inventors of the present application have found that solventscontaining a hydrogen atom absorb halogen radicals and/or halogenmolecules generated in the polymerization process. When such halogenradicals and/or halogen molecules generated in the polymerizationprocess are absorbed and exhausted by the solvent, it is difficult togenerate radicals with activity, and thus no reaction between a monomeror a macromolecule produced by the polymerization and other monomers isadditionally performed, so that the desired high molecular weightproduct cannot be obtained. In one aspect of the present application, byapplying a solvent containing no hydrogen atom as the solvent, it ispossible to prevent the exhaustion of halogen radicals and/or halogenmolecules.

In a second aspect of the present application, the step of irradiatingthe mixture comprising the solvent and the thiophene series monomer withlight may be performed in at least two steps. For example, the step ofirradiating the mixture with light may comprise a first step ofirradiating the mixture with light having a wavelength of 450 nm or lessand a second step of irradiating it with light having a wavelength ofmore than 450 nm.

For example, the first and second steps may be performed continuouslywithout interruption, or after performing the first step and stoppingthe light irradiation for a predetermined time, the second step ofirradiating it with light having a wavelength of more than 450 nm may beperformed at an appropriate time point. In addition, while the secondstep is performed, only the light having a wavelength of more than 450nm may be irradiated, or the light having a wavelength of 450 nm or lessmay also be irradiated together with the light.

In another example, the wavelength of the light irradiated in the firststep may be 100 nm or more, 150 nm or more, 200 nm or more, 250 nm ormore, 300 nm or more, or 350 nm or more, or may also be 400 nm or lessor so.

Furthermore, in another example, the wavelength of the light irradiatedin the second step may be about 900 nm or less, 850 nm or less, 800 nmor less, 750 nm or less, 700 nm or less, 650 nm or less, 600 nm or less,or 550 nm or less, or may also be 460 nm or more, 480 nm or more, or 500nm or more or so.

For generating radicals in the polymerization process of the preparationmethod of the present application and forming the desired polymer havinga high molecular weight through a chain reaction by the radicals, it isrequired that the irradiated light is absorbed by a monomer or amacromolecule formed by polymerization of the monomer to generateradicals in a chain reaction. However, the wavelength of the light thatthe monomer efficiently absorbs and the wavelength of the light that themacromolecule formed by polymerizing the monomers absorbs are differentfrom each other, and thus if the light of the same wavelength iscontinuously irradiated in the polymerization process, at least oneradical generation efficiency is lowered, so that it is not easy toproduce a polymer having a desired molecular weight.

The inventors of the present application have confirmed that they cansolve the problem and produce the desired polymer by performing thefirst step for an appropriate time and then changing the wavelength ofthe irradiated light or further irradiating it with another light toperform the second step.

The methods of the two aspects of the present application may beperformed simultaneously with each other, or may be performedindependently of each other. That is, in the preparation method ofapplying the specific solvent (solvent containing no hydrogen atom), thelight irradiation may or may not proceed in two steps described above,and in the method that the light irradiation is divided in two steps andproceeds, the solvent containing no hydrogen atom may or may not beused.

Appropriately, the two aspects are applied simultaneously, whereby thedesired polymer can be formed more efficiently.

Through such a method, the present application can produce a polymerhaving a high molecular weight of a desired level with excellentpolymerization efficiency and conversion rates without generation ofby-products or alteration of a target in the polymerization process. Inthe present application, the polymer is produced by chain polymerizationby radicals, and thus excessive doping does not occur due to halogenanions of the polymer as in an oxidation method using an oxidant,whereby the polymer can exhibit excellent solubility in varioussolvents. In addition, the preparation method of the present applicationcan form a desired polymer without requiring the use of a catalyst orwhile applying only a small amount, if necessary, so that there is no ora small amount of catalyst in the final product, whereby the desiredpolymer can be obtained with high purity without any additional processfor separating the catalyst. According to the preparation method of thepresent application, various monomers forming a polymer by the radicalreaction can be easily applied in addition to the thiophene seriesmonomer to easily and efficiently produce a copolymer of the thiopheneseries monomer and another monomer.

In both the preparation methods of the first and second aspects in thepresent application, the step of irradiating a mixture of a solvent anda thiophene-based monomer with light is performed. In this process, theratio of the thiophene-based monomer in the mixture is not particularlylimited, and the thiophene-based monomer may be applied at anappropriate ratio in consideration of the desired polymer. In oneexample, the thiophene-based monomer may have a concentration in a rangeof about 0.01 mol/L to 1 mol/L. The concentration of the thiophene-basedmonomer may be the concentration of the monomer in the solvent. Inanother example, the concentration may be about 0.05 mol/L or more, 0.1mol/L or more, 0.15 mol/L or more, 0.2 mol/L or more, 0.25 mol/L ormore, 0.3 mol/L or more, 0.35 mol/L or more, 0.4 mol/L or more, 0.45mol/L or more, or 0.5 mol/L or more. In this range, the effectivepolymerization of the monomers can be induced, and the solubility of thepolymerized polymer can also be stably maintained.

As described above, in the method for preparing a polymer of the presentapplication, it is possible to prevent consumption of halogen radicalsand halogen molecules by not applying a solvent having a hydrogen atom.Therefore, the mixture in the preparation method of the first aspectcomprises only the solvent without any hydrogen atom as the solvent, andmay be substantially free of the solvent having a hydrogen atom. Here,the fact that does not substantially apply the solvent having a hydrogenatom may mean the case where the ratio of the solvent having a hydrogenatom in the mixture is about 1 weight % or less, 0.5 weight % or less,0.1 weight % or less, 0.05 weight % or less, 0.01 weight % or less,0.005 weight % or less, 0.001 weight % or less, 0.0005 weight % or less,0.0001 weight % or less, 0.00005 weight % or less, or 0.00001 weight %or less or so. In addition, the lower limit of the ratio of the solventis 0 weight %.

As the solvent without any hydrogen atom, various solvent can be appliedwithout any particular limitation as long as it contains no hydrogenatom. Such a solvent can be exemplified by bromotrichloromethane(CBrCl₃), tetrachloromethane (CCl₄) or dibromodichloromethane (CBr₂Cl₂),and the like, but is not limited thereto.

In the preparation method of the present application, any one of theabove solvents may be selected, and if necessary, a mixed solvent of twoor more may also be applied.

In the preparation method of the present application, when the lightirradiation is divided in two steps and performed, the time for whicheach step is applied is not particularly limited. In one example, thefirst step may be performed at a level such that the total energy by theirradiated light is about 0.01 W/cm² to 20 W/cm² or so. If the totalenergy is too small, radical formation does not occur efficiently,whereas if the total energy is too high, photodegradation may occur in aproduct or the like, so that it can be adjusted to an appropriate rangein consideration of this.

In the second step, the total energy by the irradiated light may beadjusted to a level similar to that of the first step, and if the totalenergy is too small, radical formation does not occur efficiently,whereas if it is too high, photodegradation may occur in a product orthe like, so that it can be adjusted to an appropriate range inconsideration of this. On the other hand, when the light irradiated inthe second step is pulsed light to be described below, the total energyis average energy.

The light irradiation performed in the second step may proceed using apulsed light source, for example, a pulsed laser light source. Whenlight having such a long wavelength is subjected to pulse irradiation,the polymerization can be stably performed while effectively preventingphotodegradation by the irradiated light. In this case, the frequency ofthe pulsed light source may be adjusted in a range of about 1 to 20 Hzor so. In another example, the frequency may be about 2 Hz or more, 3 Hzor more, 4 Hz or more, 5 Hz or more, 6 Hz or more, 7 Hz or more, 8 Hz ormore, 9 Hz or more, or 10 Hz or more, or may also be about 19 Hz orless, 18 Hz or less, 17 Hz or less, 16 Hz or less, 15 Hz or less, 14 Hzor less, 13 Hz or less, 12 Hz or less, 11 Hz or less, or 10 Hz or lessor so.

According to one example of the present application, when the first andsecond steps are performed together, a step of additionally supplying ahalogen source at an appropriate time (for example, between the firststep and the second step) may further be performed.

While this step maintains or improves the radical generation efficiency,the polymerization process can be performed more effectively. As thehalogen source, a known compound may be applied without particularlimitation, which may be exemplified by, for example, fluorine molecules(F₂), chlorine molecules (Cl₂), bromine molecules (Br₂) or iodinemolecules (I₂), and the like, and may be, suitably, iodine molecules(I₂). In addition, the supply of halogen can be performed more smoothlyby adding perchloric acid (HClO₄) and the like together with the halogenmolecules.

In the preparation method of the present application, a polymer havingdesired molecular weight characteristics and solubility in a solvent canbe formed with excellent polymerization efficiency through such a methodwithout using a separate catalyst or other components.

The present application also relates to a polymer dispersion comprisinga polymer prepared in such a manner and a solvent.

For example, the polymer may comprise a polymerized unit of Formula 11below as the polymerized unit formed by the thiophene-based monomer ofFormulas 1 and/or 6 above.

The polymerized unit of Formula 11 below is a polymerized unit formed bylinking R₃ and R₄ moieties to each other in Formulas 1 and/or 6 above.Therefore, specific matters for R₁ and R₂ in Formula 11 below are thesame as the matters for R₁ and R₂ in Formulas 1 and 6 above.

Also, in Formula 11, n represents a degree of polymerization of thethiophene-based monomer, and is any number, which may be, for example, anumber in a range of about 4 to 200.

The content that the monomers of Formulas 1 and/or 6 are polymerized toform the unit of Formula 11 above may also be equally applied tomonomers of other formulas.

For example, when the polymerized unit is formed from the monomers ofFormulas 2 and/or 7 above, R₃ and R₄ moieties of the monomers ofFormulas 2 and/or 7 are linked to form a chain, whereby the polymerizedunit may be represented by Formula 12 below.

In Formula 12, L is the same as L in Formulas 2 and/or 7 above, and n isany number, which is, for example, a number in the range of 4 to 200.

In addition, the above content may be equally applied in a manner thatthe R₁ and R₂ moieties in the halogenated thiophene-based monomer ofFormulas 3 to 5 form a chain, and a manner that the R₁ and R₂ moietiesin the non-halogenated thiophene-based monomer of Formulas 8 to 10 forma chain.

The polymer may comprise the polymerized unit of such a thiophene-basedmonomer in an amount of about 50 mol % or more, 55 mol % or more, 60 mol% or more, 65 mol % or more, 70 mol % or more, 75 mol % or more, 80 mol% or more, 85 mol % or more, or 90 mol % or more, relative to the entirepolymerized unit of the polymer. The upper limit of such apolymerization unit ratio is not particularly limited, which may be, forexample, 100 mol % or less, 95 mol % or less, or 90 mol % or less or so.

The polymer may comprise only polymerized units of thiophene-basedmonomers having the same structure, and may also comprise polymerizedunits of two or more thiophene-based monomers having differentstructures from each other at the same time. For example, the polymermay also comprise simultaneously polymerized units that specificstructures are different from each other (for example, structures thatR₁ and R₂ in Formula 11 are different from each other, or structuresthat L in Formula 12 is different from each other), while having astructure within the category of the structure of the polymerized unitsof Formulas 11 and 12 or the category of the polymerized units ofFormulas 3 to 5 and/or Formulas 8 to 10 as described above. Here, thepolymer comprising polymerized units of two or more thiophene-basedmonomers at the same time may be in the form of a so-called randomcopolymer, block copolymer or gradient copolymer.

In addition, the polymer may further comprise other types of monomerssimultaneously in addition to the polymerized unit of thethiophene-based monomer, and in this case, the polymer may also be inthe form of a so-called random copolymer, block copolymer or gradientcopolymer.

The polymer is prepared by the above-described method of the presentapplication, which may have a large molecular weight. For example, themolecular weight of the polymer may also be about 2,000 g/mol or more,2,500 g/mol or more, 3,000 g/mol or more, 3,500 g/mol or more, 4,000g/mol or more, 4,500 g/mol or more, 5,000 g/mol or more, 5,500 g/mol ormore, 6,000 g/mol or more, 6,500 g/mol or more, 7,000 g/mol or more,7,500 g/mol or more, 8,000 g/mol or more, 8,500 g/mol or more, 9,000g/mol or more, 9,500 g/mol or more, 10,000 g/mol or more, 15,000 g/molor more, 20,000 g/mol or more, or 25,000 g/mol or more or so. Themolecular weight may be a number average molecular weight (Mn) which isa conversion value with respect to standard polystyrene measured by GPC(gel permeation chromatograph). The upper limit of the molecular weightis not particularly limited. For example, the molecular weight may alsobe about 1,000,000 g/mol or less, 500,000 g/mol or less, 100,000 g/molor less, 50,000 g/mol or less, 40,000 g/mol or less, or 30,000 g/mol orless or so.

In the dispersion, the polymer may exhibit an appropriate molecularweight distribution (PDI, ratio (Mw/Mn) of weight average molecularweight (Mw) to number average molecular weight (Mn)). For example, themolecular weight distribution may be about 1.5 or less or so. In anotherexample, the molecular weight distribution may be about 1.45 or less or1.4 or less, or may also be 1 or more, 1.05 or more, 1.1 or more, 1.15or more, 1.2 or more, 1.25 or more, or 1.3 or more or so. Such amolecular weight distribution can be obtained by the above-describedpreparation method of the present application.

In one example, the solvent included in the polymer dispersion is theabove-described solvent containing no hydrogen atom, which may bebromotrichloromethane (CBrCl₃), tetrachloromethane (CCl₄) ordibromodichloromethane (CBr₂Cl₂), but is not limited thereto.

The ratio of the polymer in the dispersion is not particularly limited,and for example, the ratio of the polymer in the dispersion may be about0.1 to 10 weight % or so.

The dispersion is prepared by the above-described method of the presentapplication, where the catalyst is not substantially applied in thepreparation process, so that it may be substantially free of a catalystcomponent. The catalyst component is usually a catalyst componentapplied to the production of a conductive polymer such as polythiophene,which is, specifically, an oxidant used in an oxidation reaction, andFeCl₃, MnO₂, CuCl₂, Fe(tosylate), Na₂S₂O₈ or the like, or a transitionmetal ligand catalyst such as1,3-bis(diphenylphosphino)propane]dichloronickel (II), and the like canbe exemplified.

Since the polymer dispersion is substantially free of the catalystcomponent, the ratio of the catalyst component in the dispersion may beabout 1 weight % or less, 0.5 weight % or less, 0.1 weight % or less,0.05 weight % or less, 0.01 weight % or less, 0.005 weight % or less,0.001 weight % or less, 0.0005 weight % or less, 0.0001 weight % orless, 0.00005 weight % or less, or 0.00001 weight % or less or so. Thelower limit of the ratio of the catalyst component is 0 weight %.

The polymer dispersion of the present application as above may beapplied to various uses, and as the ratio of unnecessary components suchas a catalyst component is minimized as described above and the polymeritself has excellent molecular weight characteristics, it can exhibitsignificantly superior performance, as compared with the existingconductive polymer, even when applied to the use to which the existingconductive polymer is applied.

The present application provides a method for preparing a polymer, and apolymer. The present application can provide a preparation method thatcan effectively produce a polymer having desired molecular weightcharacteristics and solubility in a solvent, and having a monomercomposition, which is designed freely and variously according to thepurpose, without unnecessary components with excellent polymerizationefficiency and conversion rates, and a dispersion comprising the polymerformed by the preparation method.

EXAMPLES

Hereinafter, the present application will be described in detail by wayof Examples, but the scope of the present application is not limited bythe following Examples.

1. NMR Analysis Method

¹H-NMR analysis in Examples and Synthesis Examples was performed at roomtemperature using an NMR spectrometer including a Bruker UltraShield(300 MHz) spectrometer with a triple resonance 5 mm probe. An analytewas diluted to a concentration of about 10 mg/ml or so in a solvent forNMR measurement (CDCl₃) and used, and chemical shifts were expressed inppm.

2. GPC (Gel Permeation Chromatograph)

A number average molecular weight (Mn) and a molecular weightdistribution were measured using GPC (gel permeation chromatography).Each polymer of Examples and the like is placed in a 5 mL vial anddiluted in chloroform to a concentration of about 1 mg/mL or so. Then,the standard sample for calibration and the sample to be analyzed werefiltered through a syringe filter (pore size: 0.45 μm) and thenmeasured. Empower 3 from Waters was used as an analysis program, and theweight average molecular weight (Mw) and the number average molecularweight (Mn) were each obtained by comparing the elution time of thesample with the calibration curve, and the molecular weight distribution(PDI) was calculated as the ratio (Mw/Mn). The measurement conditions ofGPC are as follows.

<GPC Measurement Conditions>

Instrument: 2414 from Waters

Column: Using three Styragel from Waters

Solvent: THF

Column temperature: 35° C.

Sample concentration: 1 mg/mL, 1 mL injection

Standard sample: Polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400,7200, 3940, 485)

3. UV-Vis Spectrum Analysis

After chloroform was placed in a transparent quartz cuvette (45 mm×12.5mm×12.5 mm) and calibrated in a wavelength region of 200 nm to 1000 nm,UV-vis spectra were performed using Agilent Technologies' Cary 50 UV-Visspectrophotometer instrument (manufacturer: Agilent Technologies,product name: Cary 50) by a method of measuring absorbance of a samplein which the polymerized sample was diluted with chloroform for thewavelength region.

Synthesis Examples 1 and 2

Compound 1 (DBuProDOT) and Compound 2 (DIBBuProDOT) in Scheme 1 belowwere synthesized in the following manner.

Synthesis of Compound 1

6 g (41.61 mmol, 1 eq) of 3,4-dimethoxythiophene and 10.187 g (54.10mmol, 1.3 eq) of 2,2-dibutyl-1,3-propanediol were dissolved, togetherwith 500 mg of p-toluenesulfonic acid, in 200 mL of toluene. The mixturewas refluxed at 120° C. and the methanol produced by a reaction(transetherification) of the reactant was removed by a 4 A typemolecular sieve filled with a soxhlet extractor. After reflux for 24hours, the mixture was quenched with water, extracted with ethyl acetateand then washed with brine, and the reactant was dried over MgSO₄. Thesolvent was evaporated by a rotary evaporator and the residue waspurified by column chromatography eluting with methylene chloride/hexane(1:4) to obtain a target (Compound 1). FIG. 1 is a ¹H-NMR spectrum ofthe target.

<¹H-NMR Spectrum of the Compound 1>

¹H-NMR (300 MHz, CDCl3); 6.42 (s, 2H), 3.85 (s, 4H), 1.46-1.15 (m, 12H),0.98-0.86 (t, 6H)

Synthesis of Compound 2

5 g (18.63 mmol, 1 eq) of Compound 1 was dissolved in chloroform andstirred together with 9.22 g (40.98 mmol, 1 eq) of n-iodosuccinimide anda few drops of acetic acid. The mixture was quenched with deionizedwater, washed with sodium thiosulfate to remove excess iodine, and thendried over MgSO₄ and evaporated under vacuum. The residue was purifiedby column chromatography eluting with methylene chloride/hexane (1:8) toobtain a target (Compound 2). FIG. 2 is a ¹H-NMR spectrum of the target.

<¹H-NMR Spectrum of the Compound 2>

¹H-NMR (300 MHz, CDCl3); 3.92 (s, 4H), 1.46-1.15 (m, 12H), 0.98-0.86 (t,6H)

Synthesis Examples 3 and 4

Compound 3 (DEHProDOT) and Compound 4 (DIDEHProDOT) in Scheme 2 belowwere synthesized in the following manner.

Synthesis of Compound 3

5 g (34.68 mmol, 1 eq) of 3,4-dimethoxythiophene and 10.9 g (41.61 mmol,1.2 eq) of 2,2-bis(bromomethyl)-1,3-propanediol were dissolved, togetherwith 500 mg of p-toluenesulfonic acid, in 200 mL of toluene. The mixturewas refluxed at 120° C. and the methanol produced by a reaction(transetherification) of the reactant was removed by a 4 A typemolecular sieve filled with a soxhlet extractor. After reflux for 24hours, the mixture was quenched with water, extracted with ethyl acetateand then washed with brine, and the reactant was dried over MgSO₄. Thesolvent was evaporated by a rotary evaporator and the residue waspurified by column chromatography eluting with methylene chloride/hexane(1:2) to obtain a target (DBrProDOT).

2.924 g (60% with oil, 73.09 mmol, 5.0 eq) of NaH was placed in a 250 mLround bottom flask, vacuum-purged and then filled three times withargon. 100 mL of anhydrous dimethylformamide (anhydrous DMF) was addedat 0° C., and the cooled solution was stirred at room temperature for 2hours. 4.19 g (32.164 mmol, 2.2 eq) of 2-ethylhexanol was dissolved in20 mL of dimethylformamide (DMF), added in drops to the NaH solution andthen stirred at room temperature for 6 hours. A mixture that 5 g (14.62mmol, 1 eq) of the resulting target (DBrProDOT) was dissolved in 20 mLof dimethylformamide (DMF) was added to the stirred product. Theprepared solution was refluxed at 80° C. for 24 hours, cooled to roomtemperature, and then quenched through 1N HCl dropping, and extractedthree times with diethyl ether. The organic layer was washed with 1N HCland brine, dried over MgSO₄ and evaporated under vacuum. The residue waspurified by column chromatography eluting with methylene chloride/hexane(1:4) to obtain a target (Compound 3). FIG. 3 is a ¹H-NMR spectrum ofthe target.

<¹H-NMR Spectrum of the Compound 3>

¹H-NMR (300 MHz, CDCl3); 6.45 (s, 2H), 4.03 (s, 4H), 3.48 (s, 4H), 3.28(d, 4H), 1.48 (s, 2H), 1.35-1.15 (m, 16H), 0.95-0.80 (m, 12H)

Synthesis of Compound 4

5 g (11.35 mmol, 1 eq) of Compound 3 was dissolved in chloroform andstirred together with 5.615 g (24.96 mmol, 2.2 eq) of n-iodosuccinimideand a few drops of acetic acid. The mixture was quenched with deionizedwater, washed with sodium thiosulfate to remove excess iodine, and thendried over MgSO₄ and evaporated under vacuum. The residue was purifiedby column chromatography eluting with methylene chloride/hexane (1:8) toobtain a target (Compound 4). FIG. 4 is a ¹H-NMR spectrum of the target.

<¹H-NMR Spectrum of the Compound 4>

¹H-NMR (300 MHz, CDCl3); 4.03 (s, 4H), 3.48 (s, 4H), 3.28 (d, 4H), 1.48(s, 2H), 1.35-1.15 (m, 16H), 0.95-0.80 (m, 12H)

Example 1

A polymer was synthesized using Compounds 1 and 2 prepared in SynthesisExamples 1 and 2. The compounds were dissolved in bromotrichloromethane(CBrCl₃) as a solvent in a molar ratio of 1:2 (Compound 1:Compound 2),and irradiated with LED light having a wavelength of 365 nm to initiatepolymerization (first step). Here, the solvent was used after purgingwith argon. After confirming that most of the monomers (Compounds 1 and2) were exhausted, the polymerization was continued by adding 2.0 mmolof I₂ and a few drops of HClO₄ and changing the light source to aq-switch pulsed laser (2 mJ/cm², 10 Hz) with a wavelength of 532 nm(second step). After aliquots were taken at regular intervals during thecourse of the reaction and diluted in chloroform, the UV-vis absorbancewas measured. The aliquots were also rinsed with sodium thiosulfate(Na₂S₂O₃) and de-doped with hydrazine (N₂H₄) to remove separate iodinemolecules, and then a neutralized polymer product was obtained, whichwas also dissolved in chloroform to perform UV-vis absorbance and GPC(gel permeation chromatograph) analyses.

FIG. 5 is UV-vis absorbance spectra identified while performing thefirst step of Example 1, and FIG. 6 is also GPC analysis resultsidentified while performing the first step.

In FIG. 5, the absorbance of the aliquots according to the irradiationtime (0, 24, 48 and 72 hours) of the LED light source with a wavelengthof 365 nm in the first stage is indicated by solid lines, and theabsorbance of the aliquots which are subjected to de-doping by 12washing for the aliquots is indicated over time (24, 48, 72 hours) bydotted lines.

From the solid lines of FIG. 5, it can be confirmed that the mainabsorption of the aliquots is found at 600 to 1,000 nm, and as theirradiation time of the LED light source increases, the main absorptionpeak is shifted to the long wavelength region. This shows that as thefirst step progresses, the conjugated length gradually increases. In thecase of the de-doped samples (dotted lines), as the irradiation time ofthe LED light became longer, absorption shifting to a longer wavelengthwas observed while vibrating in the region of 400 to 600 nm. Inparticular, the shoulder peak identified near 570 nm indicates improvedintermolecular π-π* transition of a product with a higher molecularweight. The trend shown in FIG. 5 is also consistent with the GPCanalysis results (FIG. 6). As shown in FIG. 6, it is shown that theretention time in the GPC analysis decreases as the UV irradiation (LEDlight irradiation) time increases, and the molecular weight of thepolymer increases with the consumption of the monomer (Compound 1).After LED light irradiation for 72 hours, the product (conductivepolymer) had a number average molecular weight (Mn) of about 2,200g/mol, and a molecular weight distribution (PDI) of about 1.20. Thephotograph in FIG. 6 is the precipitate of the high molecular weightcomponent generated as the polymerization proceeds. On the other hand,FIG. 10 shows a ¹H-NMR spectrum (blue line) of the polymer formed inExample 1.

Example 2

A polymer was synthesized in the same manner as in Example 1, exceptthat Compounds 3 and 4 prepared in Synthesis Examples 3 and 4 were used(molar ratio of Compounds 3 and 4 was 1:2 (Compound 4:Compound 3)). FIG.7 is UV-vis spectra identified in the first step of the process, andFIG. 8 is GPC spectra. As shown in FIGS. 7 and 8, the behavior of theUV-vis spectra and GPC spectra in the first step of the process wassimilar to Example 1. However, in the case of Example 2, the precipitatedid not occur by the bulky side chain (diethylhexylmethoxy) of Compounds3 and 4. FIG. 9 is GPC spectra in the second step of the process(irradiation of pulsed laser with 532 nm). From FIG. 9, it can beconfirmed that after pulsed laser irradiation for 12 hours, the initialnumber average molecular weight at a level of approximately 3,000 g/molgreatly increases to a level of about 29,500 g/mol (molecular weightdistribution: 1.35). On the other hand, FIG. 10 shows a ¹H-NMR spectrum(green line) of the polymer formed in Example 2.

Examples 3 to 5

The polymerization was performed in the same manner as in Example 1,using Compound 2 prepared in Synthesis Example 2 and Compound 3 preparedin Synthesis Example 3, while changing the ratios. The ratios werecontrolled to 1:2 (Compound 2:Compound 3, Example 3), 1:4 (Compound2:Compound 3, Example 4) and 1:6 (Compound 2:Compound 3, Example 5),respectively. FIGS. 11 to 13 are UV-vis spectra identified in theprocess performing the first step of Examples 3 to 5, respectively, andit can be confirmed that they show the same trend as in Example 1.

FIGS. 14 to 16 show ¹H-NMR spectra of the polymers synthesized inExamples 3 to 5.

FIG. 17 is GPC spectra identified as the second step of Example 3proceeds, and it can be confirmed that the molecular weight increases asthe irradiation time of the pulsed laser with 532 nm increases. That is,from FIG. 15, it can be confirmed that the number average molecularweight has been approximately 2,800 g/mol (molecular weightdistribution: about 1.2) at the beginning of the second step, but as thesecond step proceeds, the number average molecular weight increases to alevel of about 27,000 g/mol (molecular weight distribution: 1.25).

The invention claimed is:
 1. A method for preparing a polymer comprisinga step of irradiating a mixture containing a solvent without anyhydrogen atom, and a compound of Formula 1 below, with light:

wherein, R₁ and R₂ are each independently hydrogen, an alkyl group, analkenyl group, an alkynyl group, an alkoxy group, an alkylcarbonylgroup, an arylcarbonyl group, an arylcarbonyloxy group, analkylcarbonyloxy group, a carboxyl group or an aryl group, or are linkedto each other to form a ring structure, R₃ and R₄ are each independentlyhydrogen, a halogen atom, an alkyl group, an alkenyl group, an alkynylgroup, an alkoxy group or an aryl group, and at least one of R₃ and R₄is a halogen atom.
 2. The method for preparing a polymer according toclaim 1, wherein the solvent without any hydrogen atom isbromotrichloromethane (CBrCl₃), tetrachloromethane (CCl₄) ordibromodichloromethane (CBr₂Cl₂).
 3. The method for preparing a polymeraccording to claim 1, wherein the mixture does not include a solventwith a hydrogen atom.
 4. The method for preparing a polymer according toclaim 1, comprising a first step of irradiating the mixture containingthe solvent and the compound of Formula 1 with light having a wavelengthof 450 nm or less, and a second step of irradiating the mixture withlight by changing the wavelength of the irradiated light to more than450 nm


5. The method for preparing a polymer according to claim 4, wherein ahalogen source is further supplied between the first and second steps.6. The method for preparing a polymer according to claim 4, wherein thelight irradiated in the second step is irradiated with a pulsed lightsource.
 7. The method for preparing a polymer according to claim 1,wherein at least one of R₁ and R₂ in Formula 1 is a substituentcontaining an oxygen atom.
 8. The method for preparing a polymeraccording to claim 1, wherein the ring structure formed by linking R₁and R₂ in Formula 1 contains an oxygen atom.
 9. The method for preparinga polymer according to claim 1, wherein R₃ and R₄ in Formula 1 arehalogen atoms.
 10. The method for preparing a polymer according to claim1, wherein the compound of Formula 1 has a structure of Formula 2 below:

wherein, R₃ and R₄ are each independently hydrogen, an alkyl group, analkenyl group, an alkynyl group, an alkylcarbonyl group, an arylcarbonylgroup or an aryl group, or are linked to each other to form a ringstructure, and R₁ and R₂ are each independently hydrogen, a halogenatom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxygroup or an aryl group, and at least one of R₁ and R₂ is a halogen atom.11. The method for preparing a polymer according to claim 1 or 4,wherein the compound of Formula 1 is represented by Formula 3 below:

wherein, R₃ and R₄ are halogen atoms, and L is a divalent chain having 3to 7 chain forming atoms.
 12. The method for preparing a polymeraccording to claim 11, wherein the divalent chain contains a carbon atomand an oxygen atom.
 13. The method for preparing a polymer according toclaim 1, wherein the compound of Formula 1 is represented by Formula 4or 5 below:

wherein, R₃ and R₄ are each independently hydrogen, an alkyl group, analkenyl group, an alkynyl group, an alkoxy group, an alkylcarbonylgroup, an arylcarbonyl group, an arylcarbonyloxy group, analkylcarbonyloxy group, a carboxyl group or an aryl group, R₁ and R₂ areeach independently hydrogen, a halogen atom, an alkyl group, an alkenylgroup, an alkynyl group, an alkoxy group or an aryl group, at least oneof R₁ and R₂ is a halogen atom, and m is a number in a range of 1 to 4.14. The method for preparing a polymer according to claim 1, wherein thecompound further comprises a compound represented by Formula 6 below:

wherein, R₁ and R₂ are each independently hydrogen, an alkyl group, analkenyl group, an alkynyl group, an alkoxy group, an alkylcarbonylgroup, an arylcarbonyl group, an arylcarbonyloxy group, analkylcarbonyloxy group, a carboxyl group or an aryl group, or are linkedto each other to form a ring structure, and R₃ and R₄ are eachindependently hydrogen, an alkyl group, an alkenyl group, an alkynylgroup, an alkoxy group or an aryl group.
 15. The method for preparing apolymer according to claim 14, wherein the ratio (Halo/(Halo+H)) of themolar number (Halo) of halogen atoms included in R₃ and R₄ of Formula 1and the molar number (H) of hydrogen atoms included in R₃ and R₄ of thecompound of Formula 6 is in a range of 0.001 to 99.